Detergent compositions



March 28, 1967 e. .1. M EWAN DETERGENT COMPOSITIONS Filed June 19, 19651007., TRIMER 070 DIMER l l I 1 :IMPROVEMENT I PREDICTED EFFECT 0 QmIWWMFUQ E INVENTOR GILBERT J MCEWAN AGE United States Patent 3,311,563DETERGENT COMPOSITIONS Gilbert J. McEwan, Webster Groves, Mo., assignorto Monsanto Company, a corporation of Delaware Filed June 19, 1963, Ser.No. 288,976 I 4 Claims. (Cl. 252161) The present invention relates todetergent compositions and to methods and materials for theirmanufacture.

-More particularly, the present invention relates to novel,

synergistically active compositions which contain mixtures of certainalkylbenzene sulfonates and have unexpectedly valuable detergentproperties, and to novel compositions useful for the manufacture ofthese synergistically active compositions.

At present, by far the majority of the detergents that are sold to theconsuming public contain alkylbenzene sulfonates or other alkylaromaticsulfonates as their major detergent active ingredient. The alkylaromaticsulfonates presently utilized and sold commercially derive their alkylsubstituents, to a very large extent, from olefin polymers. The mostcommonly used olefin polymers for this purpose are propylene tetramers,propylene pentarners, and fractions intermediate between these two.

Alkylaromatic sulfonates that are derived from conventionalpolypropylene olefins, however, have alkyl chains that are highlybranched; particularly at the alpha-carbon atom. For example, sodiumdodecylbenzene sulfonate, which is prepare-d by alkylating benzene withtetrapropylene and subsequently converting the resulting alkylbenzene tothe sulfonate, contains a very high proportion of material having atertiary tx-carbon atom, i.e., an alpha carbon atom connected to threealkyl carbon atoms, as in Formula 1.

Consequently, where quick biodegradability of alkylaromatic sulfonatedetergents is desired or required, it is generally preferred thatdetergent compositions containing alkylaromatic sulfonates that havemore of a straightchain character (than do the alkylaromatic sulfonatesmade from conventional tetrapropylene) be utilized.

One class of these more biodegradable alkylaromatic sulfonates ismanufactured utilizing a hexene dimer which in turn has been made from ahexene selected from the group consisting of hexene-l, hexene-2, andhexene-3 hexenes. The numerical designation after the word hexeneindicates the position in the n-hexene molecule at which the double bondoccurs. For example, hexene-2 can be represented by the Formula 4:

HO C- H H H 3 ,311,563 Patented Mar. 28, 1967 while hexene-3 can berepresented by the Formula 5:

(5) H H H H H H HO-CO=COCH H H H H Both hexene-2 and hexene-3 occur in 2isomeric (cis, trans) forms. Although dimers of these preferred hexenescan be prepared by several well-known methods, one of the best methodswhereby they can be made in a relatively pure form is via the processdescribed in the copending United States patent application, Ser. No.126,859, filed July 26, 1961, assigned to the same assignee as thepresent patent application; which process comprises agitating internallyunsaturated hexene under pressure and in the presence of aFriedel-Crafts type catalyst.

Alkylaromatic sulfonate compounds that are manufactured from such hexenedimers, however, have the apparently inherent shortcoming of beingsomewhat inferior in certain of their surface active properties to thebest grades of otherwise comparable conventional alkylaromaticsulfonates made from certain polypropylene olefines. For example,aqueous solutions of sodium, potassium, or other alkali metal salts ofthese hexene dimer benzene sulfonates generally have significantly lessability to maintain a high, stable, aqueous foam and to clean varioussolid substrates in the presence of dissolved greases than do aqueoussolutions of the best of the sodium and potassium polypropylene benzenesulfonates. In a standard test designed to closely examine thesuitability of various water-soluble surface active agents (surfactants)for use in the formulation of high foaming hand dishwashing detergentssodium dodecylbenzene sulfonate made from hexene dimer cleaned about 10plates before the foam or lather on the surface of the test solutionbroke, while a total of 22 plates could be effectively washed by adetergent containing a sodium mono higher .alkylbenzene sulfonatederived from conventional pentapropylene (the best performer in thistest derived from polypropylene known to date) before the lather broke.(This test will be described. in more detail below.)

It has now been found that the ability of the alkali metal hexene dimermono higher alkylaromatic sulfonates to produce and maintain a highstable fo'am in the presence of greasy soils can be greatly enhanced byutilizing them in combination with appropriate amounts of a compoundhaving a structure like that of an alkali metal hexene trimer monohigher alkylaromatic sulfonate.

Actually, the invention is believed all the more surprising becausecompounds having structures like the alkali metal hexene trimer monohigher alkylaromatic sulfonates 'are, themselves, not particularlyoutstanding surfactants.

It should be emphasized at this point that the term hexene dimer as usedherein in conjunction with such terms as mono higher alkylaromatic, monohigher alkyl benzene, benzene, and the like is intended to be indicativesolely of the type of structure of the higher alkyl portion of theparticular mono higher alky'laromatic compound being discussed. Thus,the use of hexene dimer herein does not necessarily mean that thecompound was derived by dimerizing hexene, although the compound couldvery well be manufactured in this way. The essential property of thehexene dimer materials encompassed by this invention is their chemicalstructure. Thus, any material which has a structure like those compoundswhich can be manufactured by dimerizing hexene-l, hexene-2, and/orhexene-3 (under conditions which do not result in excessiverearrangements of the molecules during and after their dimerization,such as those conditions under which Friedel-Crafts dimerizations areconventionally accomplished) can be utilized in the practice of thepresent invention. Similarly, the term "ice hexene trimer as used hereinis intended to encompass those compounds having structures like thosewhich result from trimerizing hexene-l, and is not intended to belimited solely to those materials made from hexene-1. A more definitivediscussion of the actual chemical structures of the hexene dimer andhexene trimer compounds contemplated to be within the scope of thepresent invention will be presented hereinbelow.

It will also be readily appreciated by those in the art that the hexenedimer and hexene trimer mono higher alkyl aromatic materials referred tospecifically herein are not necessarily pure materials, but are rathergenerally mixtures of materials having similar molecular Weights, theaverage molecular Weight of such mixtures being the ones desired anddiscussed specifically herein as though the materials were fairly pure.

In accordance with the present invention, it has been found thatcompositions containing alkali metal hexene dimer mono higheralkylarornatic sulfonates and alkali metal hexene trimer mono higheralkylaromatic sulfonates in weight ratios, respectively, of from about1:4 to about 4:1, have greatly improved detergency characteristics whenthey are dissolved in water, as compared with aqueous solutions of thepure materials. Preferred weight ratios of these materials in suchcompositions are from about 7:13 to about 13:7, respectively.

The alkali metal hexene trimer mono higher alkylaromatic sulfonatecomponent of the final sulfonate compositions of this invention can bemanufactured by first alkylating an appropriate aromatic compound withan olefin derived by polymerizing (trimerizing) hexene-l under pressureand in the presence of a Friedel-Crafts type catalyst; as, for example,in accordance with the processes described in the co-pending patentapplication, Ser. No. 152,655, filed Nov. 15, 1961, assigned to the sameassignee as the present patent application; and subsequently sulfonatingand neutralizing the resulting hexene trimer mono higher alkylaromaticintermediate compound. The term mono higher alkyl aromatic is hereinintended to encompass those compounds having a single six-memberedaromatic hydrocarbon nucleus (or ring) and a single higher alkyl sidechain attached to the ring through a CC bond. The term higher alkyl isintended to include saturated alkyl chains containing from about 8 toabout 30, and preferably from about 10 to about 20 carbon atoms perhigher alkyl chain. However, because of the particular subject matter ofthis invention, generally the term higher alkyl as used herein will bedirected to compounds having either about 12 or about 18 carbon atoms.In addition to the single higher alkyl chain, the mono higher a'lkylaromatic compounds encompassed by this invention can also have attachedto the aromatic nucleus from 1 to 4 lower alkyl groups, each containingfrom 1 to 4 carbon atoms, although a preferred class of mono higheralkyl aromatic compounds includes Specifically the mono higher alkylbenzenes, toluenes, and xylenes. Of these, the mono higher alkylbenzenes are particularly preferred. The compositions and processes ofthe present invention will be particularly concerned herein with thepreferred mono higher alkyl benzenes, toluenes, and xylenes, as well astheir corresponding alkali metal sulfonates. For purposes of the presentinvention, the term alkali metal encompasses the ammonium (NI-1 cationas well as sodium, potassium, lithium, rubidium, cesium, and francium.Of these, ammonium, sodium, and potassium are generally preferredbecause of their relatively low cost.

As it was mentioned heretofore, the alkali metal mono hexene dimeraromatic sulfonates to which this invention is directed are those havingstructures like the compounds that can be derived by dimerizinghexene-1, hexene-2, or hexene-3, or mixtures thereof. These materialshave a single higher alkyl chain that contains, on the average, about 12carbon atoms. The fact that the higher 'alkyl (dodecyl) portion of aparticular dodecylbenzene, for

example, has the desired structure (rather than that of one derived fromconventional sources of dodecyl alkyl groups) can be ascertained viarecognized analytical techniques. Some of these techniques will bedescribed in greater detail herein subsequently.

The alkali metal mono hexene trimer aromatic sulfonates of thisinvention (in which the higher alkyl chain averages C has a structurelike those derived by trimerizing hexene-1, hexene-2, hexene-3, ormixtures thereof. It, too, can be distinguished from conventional Calkylaromatic sulfonates by means of conventional analytical techniques.For example, by employing a recognized nuclear magnetic resonance(n.m.r.) technique in which, by means of a Varian Model A-60spectrometer with spinning 5 mm. bore glass sample tubes at ambienttemperatures (about 32 C.), and using tetramethylsilane as a standard,recording peak positions in cycles per second and ppm. of the magneticfield, it is possible (by subsequently comparing the areas under therespective peaks in the n.m.r. spectra) to distinguish with fairly highaccuracy the minimum number of methylene (-CH groups in a givenalkylaromatic hydrocarbon or its corresponding sulfonate sample. Thus,for the preferred mono hexene dimer alkylaromatic compounds that areuseful in the present invention it has been found that the minimumnumber of CH groups or units is between about 6.0 and about 9.0, whilethe percent fraction of molecules in the mono hexene dimer aromaticcompounds of this invention that have branching on the acarbon atom isbetween about 25 and about 50%, and is preferably between about 35 andabout 46%. These figures are to be compared with similar data fordodecylbenzene, for example, derived from conventional tetrapropylenewhich has at most about 5.6 CH groups per molecule and more than 65% ofits molecules having branching on the oc-CaIbOI1 atom. Correspondingdata for alkylbenzene prepared by alkylating benzene with conventionaln-dodecene-l shows the minimum number of CH groups equal to 9.8 andessentially no branching on the a-carbon atom. The hexene trimer monohigher alkylaromatic hydrocarbons and their corresponding sulfonatesthat are contemplated to be within the scope of this invention containfrom about 9 to about 15 methylene groups. The percent fraction ofmolecules in these materials that have branching on the u-CBIbOIl atomis from about 5% to about 50%, and preferably is from about 5% to about35%, according to the n.m.r. analysis. Thus, since they have such arelatively high proportion of their carbon atoms in the form ofmethylene (CH groups, the higher alkyl portion of the hexene dimer andhexene trimer mono higher alkylaromatic hydrocarbons (and theircorresponding sulfonates) of this invention can be said to be largelystraight chain in character.

The unexpected synergistic results that can be obtained by practicingthe present invention is illustrated by the drawing. A study of thedrawing reveals that, whereas data (resulting from the use of a standardtest involving the cleaning of synthetically soiled dinner plates usingthe individual relatively pure ingredients) indicates that it would beexpected that a mixture consisting of a blend of an amount of sodiumhexene dimer benzene sulfonate (in this instance derived from hexene-2)with an equal amount, by weight, of sodium hexene trimer benzenesulfonte (in this instance derived from hexene-l) would wash about 14plates, it was found that the actual number of plates that could bewashed with such a mixture was about 27. Similarly, a mixture consistingof 75 weight percent of the same sodium hexene dimer ben zene sulfonateand 25 weight percent of the same sodium hexene trimer benzene sulfonatesuccessfully washed about 25 plates, although from the plate washingdata for thepure individual ingredients of this mixture in this test,the mixture would be expected to successfully wash only about half thismany plates.

The standard hand dishwashing test mentioned above involves the washingby hand of nine-inch dinner plates which are pre-soi led with oneteaspoonful each of a synthetic soil mixture consisting of 75 weightpercent of shortening and 25 weight percent of flour. Washing of theplates is performed (using a dishcloth to remove the synthetic soil) in4 liters of water having an initial temperature of about 50 C. andcontaining 0.075 weight percent of the surfactant or surfactant mixturebeing tested. The number of plates washed (for the data above, and inthe drawing) is determined by the number of plates which can be cleanedin the normal fashion by the time the lather on the surface of thedishpan has broken to the extent that less than half of the surfaceremains covered with lather. The manipulative procedures of this testare described in greater detail in the Proceedings of the 43rd AnnualMeeting of the Chemical Specialties Manufacturers Association, December1956; Procedure No. 3, page 191.

While the valuable synergistic properties of the surfactant compositionsof the present invention are most evident when these compositions areutilized (in aqueous media) in the presence of greases, thesecompositions are nevertheless also useful as general purpose detergents,dispersing agents, wetting agent, and the like, even in the absence ofgreases. For example, they can be advantageously utilized in combinationwith any materials that can ordinarily be utilized in combination withany conventional alkali metal tetrapropylene-derived aromatic sulfonates[such as sodium tetrapropylene (dodecyl) benzene sulfonate]. Suchmaterials are well-known in the art and need not be detailed here. Thesurfactant compositions of this invention can also be advantageouslyused in combination with alkali metal tetrapropylene alkylaromaticsulfonates, if desired. The following data is illustrative of the bro-adranges of applicability, as well as the high degree of utility invarious types of applications, which the surfactant com-positions ofthis invention have.

In Table I, a composition containing 50 weight percent of sodium hexenedimer benzene sulfonate (wherein the hexene dimer was made by dimerizinga blend of hexene- 2 and hexene-3) and 50 weight percent sodium hexenetrimer benzene sulfonate (wherein the hexene trimer was manufactured bytrimerizing hexene-1 in the presence of aluminum chloride), is comparedin equal concentrations (in water) in the various standard tests shownwith a commercial sodium pentadeeylbenzene sulfonate (made frompentapropylene).

TABLE I.-SURFACE ACTIVE AGENT EVALUATION DATA Concen- Product Conven-Test tration of this tional (weight invention Surfacpercent) taut 1 0.25 118 116 Ross-Miles Lather B 0. 1 25 p.p m p 16.7 19. 7 150 p.p.m 10.2 5. 9 Draves-Clarkson Wetting Time 0.125 17 8. 4 (seconds) 0. 063 33 240.031 79 47 0.25 27. S 30. 1 Surface Tension 4 (dynes/em.) 0. 10 26. 330. 6 0.05 25. 7 31.0 0.25 1. 2 5. 2 Interl'acial Tension 4 (dynes/cm.)0.10 1.1 6. 1 0. 05 1. 0 6. 6 V 0.25 +2.1 -4. 2 Spreading Coefficient 40. 10 +2. 3 5. 6 0. 05 +5. 2 5. 2

1 Sodium pentadecylbenzeue sulfonate derived from conventionaltetrapropylene (highly branched).

1x1 300 ppm. hard water. Test described by Jay C. Harris 111 Evaluationof Surface Active Agents ASTM Bulletin, May 1946.

a 50 0. Values were taken 5 minutes after the lather was formed.

4 Room temperature, in distilled water.

One method for manufacturing the surfactant mixtures or blends of thisinvention is by simply intermixing one of the aforementioned alkalimetal mono hexene dimer benzene, toluene, or xylene sulfonates that canbe used in the practice of this invention with an appropriate alkalimetal mono hexene trimer benzene, toluene, or xylene sulfonate such asthose delineated hereinbefore in such proportions that one of thevaluable synergistic mixtures of this invention result therefrom; forexample, by blending an amount of potassium mono hexene dimer toluenesulfonate (made from hexene-2) with an equal amount, by weight, ofpotassium mono hexene trimer toluene sulfonate (made from hexene-1); bypreparing a mixture consisting of 50 weight percent of ammonium monohexene dimer benzene sulfonate (made from hexene-3), and 50 weightpercent of sodium mono hexene trimer toluene sulfonate (made fromhexene-1); or blending 67 parts byweight of sodium mono hexene dimerxylene sulfonate (made from a blend of hexene-2 and hexene-3) with 33parts by weight of one of the desired sodium mono hexene trimer benzenesulfonates.

Another convenient way in which the valuable surfactant mixtures of thisinvention can be manufactured is via a mixed alkylation procedure suchas that illustrated below in the example.

Example A mixture consisting of 1670 parts by weight of hexene dimer(prepared from a mixture of hexene-1, hexene-2, and hexene-3, byfollowing procedure described in EX- ample I of US. patent application,Ser. No. 126,859, referred to above), and 2510 parts by weight of hexenetrimer (prepared from hexene-l by following the procedure described inExample I of US. patent application, Ser. No. 152,655, also referred toabove) is added dropwise over a period of aboutl hour to 10,000 parts byweight of dry benzene which has previously been saturated with gaseousHCl, and which also contains dispersed therein, 130 parts by weight ofpowdered aluminum chloride. During the addition of the hexenedimerhexene trimer mixture, the temperature of the reaction mixture isheld between about 35 C. and about 37 C. The reaction mixture is alsocontinuously agitated during said addition. Agitation is continued aftersaid addition for about 15 minutes or until the reaction (alkylation) ispractically complete. The resulting reaction mass is then allowed toseparate into two layers; an upper alkylated layer and a lower catalystcomplex layer. The upper alkylated layer is then recovered and washedthoroughly with water and then fractionally distilled in vacuo.Fractional distillation, at about 2 mm. of mercury vacuum yields weightpercent of desired product boiling between about and about C., based onthe total amount of hexene dimer-hexene trimer mixture initially chargedinto the benzene. The product from the distillation is an approximatelyequimolar mixture of hexene dimer benzene and hexene trimer benzene.

Sulfonation of the resulting product from the foregoing distillation isaccomplished by charging 2000 parts by weight of the mixture ofalkylbenzenes into a conventional glass-lined reaction vessel, loweringthe temperature of the mixture to about 10 C., and then adding,dropwise, 2500 parts of 20% oleum with constant agitation. During theaddition of the oleum, the temperature of the sulfonation reaction massis maintained below about 20 C. After all of the oleum is added, thereaction mass is agitated for an additional hour while the temperatureof the reaction mass is permitted to rise to 40 C. Then 200 parts ofwater are added. After an additional 10 minutes of agitation, duringwhich time the temperature within the reaction vessel is maintainedbelow about 60 C., the agitation is halted and the mixture permitted tosettle into two layers. The lower spent sulfuric acid layer isdiscarded, while the upper layer is recovered and found to be anapproximately equimolar mixture of mono hexene dimer benzene sulfonicacid and hexene trimer benzene sulfonic acid. The mixture of sulfonicacids is subsequently neutralized with a 50 weight percent aqueoussolution of sodium hydroxide 7 in a conventional manner to yield one ofthe valuable synergistic surfactant mixtures of the present invention.

While the foregoing example was of necessity restricted to themanufacture of an equimolar mixture of sodium mono hexene dimer benzenesulfonate with sodium mono hexene trimer benzene sulfonate, such anoverall procedure can be utilized to manufacture practically any of thesurfactant mixtures of this invention.

The procedure described in the foregoing example represents perhaps themost economical and practical manner in which the present invention canbe practiced. For example, mixtures or blends of an appropriate hexenedimer with an appropriate hexene trimer (in the same or similar molar orweight ratios as they appear in the surfactant mixtures of thisinvention) and/or mixtures or blends of the mono hexene dimer benzene,toluene or xylene with the mono hexene trimer benzene, toluene orxylenes to which the present invention is directed (in approximately thesame molar or weight ratio as they appear in the final surfactantmixtures of the invention) can readily be sold to detergentmanufacturers, who in turn can convert the various intermediate mixturesinto the final surfactant mixtures for use in their own detergentproducts. Thus, blends or mixtures of hexene dimer with hexene trimermade from hexene-1, hexene-2, and/or hexene-3 (in Weight ratios of fromabout 80:20 to about :80, respectively, and preferably from about 13:7to about 7:13, respectively) and/or blends or mixtures of thecorresponding mono hexene dimer benzene, toluene, or xylene with monohexene trimer benzene, toluene, or xylene (in similar weight ratios),which are valuable intermediate compositions useful in the preparationof the final surfactant mixtures of this invention, and which alsorepresent articles or materials likely to be sold in commerce in thepractice of the invention, also constitute preferred embodiments of thepresent invention. The following specific examples are illustrative ofthese preferred intermediate compositions.

Example Hexene Dimer Fraetion Ilexene Trimer Fraction 1 75% hexene dimerhexene (lin1er 60% hexene dimer 75% hexene dimer benzene.- hexene dimerbenzene... 75% hexene dimer toluene.... hexene dimer toluene 50% hexenedimer toluei 75% hexene dimer xylen 25% hexene dimer xylene. 25% hexenedimer xylene.

- 50% hexene dimer xylene.

50% hexene dimer beuzene.-

1 Percentages given are Weight percentages. In each example, hexenedimer and hexene trimer can be made from either pure hexene-1, hexene-2, or hexene3, or mixtures thereof, or by any other means whereby compounds having structures like those derived from these hexencs can bemade.

Mixtures of the sulfonic acids corresponding to the mixtures of alkalimetal mono hexene dimer aromatic sulfonates with alkali metal monohexene trimer aromatic sulfonates which were described hereinbefore asbeing within the scope of the present invention are also preferredembodiments of the invention.

What is claimed is:

1. A detergent composition consisting essentially of a mixture of afirst mono higher alkyl aromatic material having a single six-memberaromatic nucleus selected from the group consisting of alkali metal monohexene dimer alkylaromatic sulfonates and mono hexene dimeralkylaromatic sulfonic acids with a second mono higher alkyl aromaticmaterial having a single six-member aromatic nucleus selected from thegroup consisting of alkali metal mono hexene trimer alkylaromaticsulfonates and mono hexene trimer alkylaromatic sulfonic acids, whereinthe hexene dimer alkyl portion of said first mono higher alkylaromaticmaterial is straight chain in character and has branching on from about25 to about 50% of its a-carbon atoms and the hexene trimer alkylportion of said second mono higher alkylarom-atic material is straightchain in character and has branching on from auout 5 to about 50% of itstat-carbon atoms; the amount of said first mono higher alkyl aromaticmaterial in said mixture being from about 20 to about Weight percent,based on the total weight of said mixture.

2. A detergent composition as in claim 1, wherein the amount of saidfirst mono higher alkylaromaitc material in said mixture is from about35 to about 65 weight percent, based on the total weight of saidmixture, and wherein said aromatic nucleus is selected from the groupconsisting of benzene, xylene, and toluene.

3. A detergent composition consisting essentially of a mixture of asodium mono hexene dimer benzene sulfonate with a sodium mono hexenetrimer benzene sulfonate, wherein the hexene dimer and hexene trimerportions, respectively, are largely straight chain in character and havebranching on from about 25 to about 50% of their ot-carbon atoms; theamount of said sodium mono hexene dimer benzene sulfonate in saidmixture being from about 35 to about 65 weight percent of said mixture.

4. A detergent composition consisting essentially of a mixture of a monohexene dimer benzene sulfonate selected from the group consisting ofammonium, sodium, and potassium mono hexene dimer benzene sulfonates anda mono hexene trimer benzene sulfonate selected from the groupconsisting of ammonium, potassium, and sodium mono hexene trimer benzenesulfonates wherein the hexene dimer and hexene trimer portions,respectively, have branching on from about 25 to about 50% of their(Z-CaI'bQnS; the amount of said mono hexene dimer benzene sulfonate insaid mixture being from about 35 to about 65% of said mixture.

References Cited by the Examiner UNITED STATES PATENTS LEON D. ROSDOL,Primary Examiner.

ALBERT T. MEYERS, Examiner.

W. E. SCHULZ, Assistant Examiner.

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A MIXTURE OF AFIRST MONO HIGHER ALKYL AROMATIC MATERIAL HAVING A SINGLE SIX-MEMBERAROMATIC NUCLEUS SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL MONOHEXENE DIMER ALKYLAROMATIC SULFONATES AND MONO HEXENE DIMERALKYLAROMATIC SULFONIC ACIDS WITH A SECOND MONO HIGHER ALKYL AROMATICMATERIAL HAVING A SINGLE SIX-MEMBER AROMATIC NUCLEUS SELECTED FROM THEGROUP CONSISTING OF ALKALI METAL MONO HEXENE TRIMER ALKYLAROMATICSULFONATES AND MONO HEXENE TRIMER ALKYLAROMATIC SULFONIC ACIDS, WHEREINTHE HEXENE DIMER ALKYL PORTION OF SAID FIRST MONO HIGHER ALKYLAROMATICMETERIAL IS STRAIGHT CHAIN IN CHARACTER AND HAS BRANCHING ON FROM ABOUT25 TO ABOUT 50% OF ITS A-CARBON ATOMS AND THE HEXENE TRIMER ALKYLPORTION OF SAID SECOND MONO HIGHER ALKYLAROMATIC MATERIAL IS STRAIGHTCHAIN IN CHARACTER AND HAS BRANCHING ON FROM ABOUT 5 TO ABOUT 50% OF ITSA-CARBON ATOMS; THE AMOUNT OF SAID FIRST MONO HIGHER ALKYL AROMATICMATERIAL IN SAID MIXTURE BEING FROM ABOUT 20 TO ABOUT 80 WEIGHT PERCENT,BASED ON THE TOTAL WEIGHT OF SAID MIXTURE.